DE68906638T2 - Verfahren zur herstellung von 4-methylpyrazolen. - Google Patents

Verfahren zur herstellung von 4-methylpyrazolen.

Info

Publication number: DE68906638T2
Authority: DE; Germany
Prior art keywords: pyridyl; methyl; reaction; group; chloro
Prior art date: 1988-10-26
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.): Expired - Fee Related

Application number

DE8989310624T

Other languages

German (de)

English (en)

Other versions

DE68906638D1 (de

Inventor

Isao C O Onoda Factory Hashiba

Yoshihiro C O Central Iwasawa

Hiroshi C O Central R Murakami

Fumio C O Central Resea Suzuki

Kenji C O Central Resea Suzuki

Susumu C O Central Re Yamamoto

Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)

Nissan Chemical Corp

Original Assignee

Nissan Chemical Corp

Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)

1988-10-26

Filing date

1989-10-17

Publication date

1993-09-16

1989-10-17 Application filed by Nissan Chemical Corp filed Critical Nissan Chemical Corp

1993-06-24 Application granted granted Critical

1993-06-24 Publication of DE68906638D1 publication Critical patent/DE68906638D1/de

1993-09-16 Publication of DE68906638T2 publication Critical patent/DE68906638T2/de

2009-10-18 Anticipated expiration legal-status Critical

Status Expired - Fee Related legal-status Critical Current

Links

238000004519 manufacturing process Methods 0.000 title claims description 7
-1 2-ethylphenyl Chemical group 0.000 claims description 120
238000006243 chemical reaction Methods 0.000 claims description 57
HWRRRIKZPDRSFG-UHFFFAOYSA-N 2,3-dichloro-2-methylpropanal Chemical compound ClCC(Cl)(C)C=O HWRRRIKZPDRSFG-UHFFFAOYSA-N 0.000 claims description 50
150000002429 hydrazines Chemical class 0.000 claims description 25
238000000034 method Methods 0.000 claims description 24
239000011541 reaction mixture Substances 0.000 claims description 21
XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
239000002904 solvent Substances 0.000 claims description 20
RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 18
VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 18
ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 18
RIKMMFOAQPJVMX-UHFFFAOYSA-N fomepizole Chemical compound CC=1C=NNC=1 RIKMMFOAQPJVMX-UHFFFAOYSA-N 0.000 claims description 16
QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 15
239000003795 chemical substances by application Substances 0.000 claims description 13
OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 10
125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 8
RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 claims description 6
UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 claims description 6
JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-Diisopropylethylamine (DIPEA) Chemical compound CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 claims description 6
JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 6
QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 claims description 6
LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 claims description 5
125000000217 alkyl group Chemical group 0.000 claims description 5
239000003054 catalyst Substances 0.000 claims description 5
GGSUCNLOZRCGPQ-UHFFFAOYSA-N diethylaniline Chemical compound CCN(CC)C1=CC=CC=C1 GGSUCNLOZRCGPQ-UHFFFAOYSA-N 0.000 claims description 5
VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 5
125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 5
239000000126 substance Substances 0.000 claims description 5
QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 claims description 4
SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 4
BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical compound CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 claims description 4
IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 4
125000004432 carbon atom Chemical group C* 0.000 claims description 4
MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 4
XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 4
150000007530 organic bases Chemical class 0.000 claims description 4
239000003960 organic solvent Substances 0.000 claims description 4
VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 4
XEZNGIUYQVAUSS-UHFFFAOYSA-N 18-crown-6 Chemical compound C1COCCOCCOCCOCCOCCO1 XEZNGIUYQVAUSS-UHFFFAOYSA-N 0.000 claims description 3
ZZKDGABMFBCSRP-UHFFFAOYSA-N 3-ethyl-2-methylpyridine Chemical compound CCC1=CC=CN=C1C ZZKDGABMFBCSRP-UHFFFAOYSA-N 0.000 claims description 3
SVYKKECYCPFKGB-UHFFFAOYSA-N N,N-dimethylcyclohexylamine Chemical compound CN(C)C1CCCCC1 SVYKKECYCPFKGB-UHFFFAOYSA-N 0.000 claims description 3
XTAZYLNFDRKIHJ-UHFFFAOYSA-N n,n-dioctyloctan-1-amine Chemical compound CCCCCCCCN(CCCCCCCC)CCCCCCCC XTAZYLNFDRKIHJ-UHFFFAOYSA-N 0.000 claims description 3
239000003444 phase transfer catalyst Substances 0.000 claims description 3
UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 3
JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 3
IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 claims description 3
YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 claims description 3
RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 claims description 2
125000004201 2,4-dichlorophenyl group Chemical group [H]C1=C([H])C(*)=C(Cl)C([H])=C1Cl 0.000 claims description 2
125000004215 2,4-difluorophenyl group Chemical group [H]C1=C([H])C(*)=C(F)C([H])=C1F 0.000 claims description 2
125000004182 2-chlorophenyl group Chemical group [H]C1=C([H])C(Cl)=C(*)C([H])=C1[H] 0.000 claims description 2
125000004198 2-fluorophenyl group Chemical group [H]C1=C([H])C(F)=C(*)C([H])=C1[H] 0.000 claims description 2
125000004204 2-methoxyphenyl group Chemical group [H]C1=C([H])C(*)=C(OC([H])([H])[H])C([H])=C1[H] 0.000 claims description 2
125000004105 2-pyridyl group Chemical group N1=C([*])C([H])=C([H])C([H])=C1[H] 0.000 claims description 2
125000004179 3-chlorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C(Cl)=C1[H] 0.000 claims description 2
125000004180 3-fluorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C(F)=C1[H] 0.000 claims description 2
125000004207 3-methoxyphenyl group Chemical group [H]C1=C([H])C(*)=C([H])C(OC([H])([H])[H])=C1[H] 0.000 claims description 2
125000003349 3-pyridyl group Chemical group N1=C([H])C([*])=C([H])C([H])=C1[H] 0.000 claims description 2
125000004860 4-ethylphenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])C([H])([H])[H] 0.000 claims description 2
125000001255 4-fluorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1F 0.000 claims description 2
125000004172 4-methoxyphenyl group Chemical group [H]C1=C([H])C(OC([H])([H])[H])=C([H])C([H])=C1* 0.000 claims description 2
125000000339 4-pyridyl group Chemical group N1=C([H])C([H])=C([*])C([H])=C1[H] 0.000 claims description 2
LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 2
VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 2
CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 2
HTZCNXWZYVXIMZ-UHFFFAOYSA-M benzyl(triethyl)azanium;chloride Chemical compound [Cl-].CC[N+](CC)(CC)CC1=CC=CC=C1 HTZCNXWZYVXIMZ-UHFFFAOYSA-M 0.000 claims description 2
229940117389 dichlorobenzene Drugs 0.000 claims description 2
SHFJWMWCIHQNCP-UHFFFAOYSA-M hydron;tetrabutylazanium;sulfate Chemical compound OS([O-])(=O)=O.CCCC[N+](CCCC)(CCCC)CCCC SHFJWMWCIHQNCP-UHFFFAOYSA-M 0.000 claims description 2
125000000040 m-tolyl group Chemical group [H]C1=C([H])C(*)=C([H])C(=C1[H])C([H])([H])[H] 0.000 claims description 2
125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
125000003261 o-tolyl group Chemical group [H]C1=C([H])C(*)=C(C([H])=C1[H])C([H])([H])[H] 0.000 claims description 2
125000003854 p-chlorophenyl group Chemical group [H]C1=C([H])C(*)=C([H])C([H])=C1Cl 0.000 claims description 2
125000000636 p-nitrophenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)[N+]([O-])=O 0.000 claims description 2
229920002523 polyethylene Glycol 1000 Polymers 0.000 claims description 2
235000019260 propionic acid Nutrition 0.000 claims description 2
IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 2
IBWGNZVCJVLSHB-UHFFFAOYSA-M tetrabutylphosphanium;chloride Chemical compound [Cl-].CCCC[P+](CCCC)(CCCC)CCCC IBWGNZVCJVLSHB-UHFFFAOYSA-M 0.000 claims description 2
WAGFXJQAIZNSEQ-UHFFFAOYSA-M tetraphenylphosphonium chloride Chemical compound [Cl-].C1=CC=CC=C1[P+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 WAGFXJQAIZNSEQ-UHFFFAOYSA-M 0.000 claims description 2
239000008096 xylene Substances 0.000 claims description 2
YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims 3
FFOVFIRMBLLEJP-UHFFFAOYSA-N 2,3,4,7-tetrahydro-1h-purine Chemical compound N1CNC=C2NC=NC21 FFOVFIRMBLLEJP-UHFFFAOYSA-N 0.000 claims 1
150000001470 diamides Chemical class 0.000 claims 1
229910052739 hydrogen Inorganic materials 0.000 claims 1
239000001257 hydrogen Substances 0.000 claims 1
125000001037 p-tolyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 claims 1
239000000203 mixture Substances 0.000 description 37
HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 36
WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 24
238000003756 stirring Methods 0.000 description 17
239000000243 solution Substances 0.000 description 15
SZQCPPRPWDXLMM-UHFFFAOYSA-N 1,4-dimethylpyrazole Chemical compound CC=1C=NN(C)C=1 SZQCPPRPWDXLMM-UHFFFAOYSA-N 0.000 description 14
239000000284 extract Substances 0.000 description 13
239000010410 layer Substances 0.000 description 12
235000011121 sodium hydroxide Nutrition 0.000 description 12
HDZGCSFEDULWCS-UHFFFAOYSA-N monomethylhydrazine Chemical compound CNN HDZGCSFEDULWCS-UHFFFAOYSA-N 0.000 description 11
238000004817 gas chromatography Methods 0.000 description 10
KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
239000012044 organic layer Substances 0.000 description 8
238000004458 analytical method Methods 0.000 description 7
238000011282 treatment Methods 0.000 description 7
OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 6
CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine hydrate Chemical compound O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 6
BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 6
STNJBCKSHOAVAJ-UHFFFAOYSA-N Methacrolein Chemical compound CC(=C)C=O STNJBCKSHOAVAJ-UHFFFAOYSA-N 0.000 description 5
238000000605 extraction Methods 0.000 description 5
239000007864 aqueous solution Substances 0.000 description 4
229960004285 fomepizole Drugs 0.000 description 4
150000007529 inorganic bases Chemical class 0.000 description 4
239000011259 mixed solution Substances 0.000 description 4
WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
150000001338 aliphatic hydrocarbons Chemical class 0.000 description 3
150000004945 aromatic hydrocarbons Chemical class 0.000 description 3
230000015572 biosynthetic process Effects 0.000 description 3
238000004821 distillation Methods 0.000 description 3
238000001914 filtration Methods 0.000 description 3
238000004811 liquid chromatography Methods 0.000 description 3
229910000027 potassium carbonate Inorganic materials 0.000 description 3
235000011181 potassium carbonates Nutrition 0.000 description 3
TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 3
235000011118 potassium hydroxide Nutrition 0.000 description 3
125000004076 pyridyl group Chemical group 0.000 description 3
229910000029 sodium carbonate Inorganic materials 0.000 description 3
235000017550 sodium carbonate Nutrition 0.000 description 3
239000007858 starting material Substances 0.000 description 3
XXUVZEUVHCFPAP-UHFFFAOYSA-N 1-butyl-4-methylpyrazole Chemical class CCCCN1C=C(C)C=N1 XXUVZEUVHCFPAP-UHFFFAOYSA-N 0.000 description 2
LKPIHZYSWUIMCZ-UHFFFAOYSA-N 2,3-dibromo-2-methylpropanal Chemical compound BrCC(Br)(C)C=O LKPIHZYSWUIMCZ-UHFFFAOYSA-N 0.000 description 2
IZRKUJREXIKAQM-UHFFFAOYSA-N 2,3-dichloropropanal Chemical compound ClCC(Cl)C=O IZRKUJREXIKAQM-UHFFFAOYSA-N 0.000 description 2
FYWSABALQBFSCW-UHFFFAOYSA-N 2,4-dimethylpyrazole-3-carboxylic acid Chemical compound CC=1C=NN(C)C=1C(O)=O FYWSABALQBFSCW-UHFFFAOYSA-N 0.000 description 2
ZWHANXMMZRUTAY-UHFFFAOYSA-N 2-chloroprop-2-enal Chemical compound ClC(=C)C=O ZWHANXMMZRUTAY-UHFFFAOYSA-N 0.000 description 2
ADHPAHRITFHGGD-UHFFFAOYSA-N 4-methyl-1-phenylpyrazole Chemical class C1=C(C)C=NN1C1=CC=CC=C1 ADHPAHRITFHGGD-UHFFFAOYSA-N 0.000 description 2
PFGFNYQYISMNJD-UHFFFAOYSA-N 4-methyl-1-propylpyrazole Chemical class CCCN1C=C(C)C=N1 PFGFNYQYISMNJD-UHFFFAOYSA-N 0.000 description 2
KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 2
UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
150000001298 alcohols Chemical class 0.000 description 2
150000004982 aromatic amines Chemical class 0.000 description 2
238000009835 boiling Methods 0.000 description 2
230000000052 comparative effect Effects 0.000 description 2
235000014113 dietary fatty acids Nutrition 0.000 description 2
238000001704 evaporation Methods 0.000 description 2
230000008020 evaporation Effects 0.000 description 2
239000000194 fatty acid Substances 0.000 description 2
229930195729 fatty acid Natural products 0.000 description 2
150000004665 fatty acids Chemical class 0.000 description 2
239000000706 filtrate Substances 0.000 description 2
238000009776 industrial production Methods 0.000 description 2
239000000543 intermediate Substances 0.000 description 2
238000011835 investigation Methods 0.000 description 2
HKOOXMFOFWEVGF-UHFFFAOYSA-N phenylhydrazine Chemical compound NNC1=CC=CC=C1 HKOOXMFOFWEVGF-UHFFFAOYSA-N 0.000 description 2
229940067157 phenylhydrazine Drugs 0.000 description 2
150000003217 pyrazoles Chemical class 0.000 description 2
150000003222 pyridines Chemical class 0.000 description 2
150000003839 salts Chemical class 0.000 description 2
238000003786 synthesis reaction Methods 0.000 description 2
ZTPAUBJZUBGGEY-UHFFFAOYSA-N (2,4-dichlorophenyl)hydrazine Chemical compound NNC1=CC=C(Cl)C=C1Cl ZTPAUBJZUBGGEY-UHFFFAOYSA-N 0.000 description 1
CCHJMGDYNLOYKM-UHFFFAOYSA-N (2,6-dimethylphenyl)hydrazine Chemical compound CC1=CC=CC(C)=C1NN CCHJMGDYNLOYKM-UHFFFAOYSA-N 0.000 description 1
GHGPIPTUDQZJJS-UHFFFAOYSA-N (2-chlorophenyl)hydrazine Chemical compound NNC1=CC=CC=C1Cl GHGPIPTUDQZJJS-UHFFFAOYSA-N 0.000 description 1
JHPOWXCLWLEKBY-UHFFFAOYSA-N (2-ethylphenyl)hydrazine Chemical compound CCC1=CC=CC=C1NN JHPOWXCLWLEKBY-UHFFFAOYSA-N 0.000 description 1
FGODPVCKFLEVFG-UHFFFAOYSA-N (2-methoxyphenyl)hydrazine Chemical compound COC1=CC=CC=C1NN FGODPVCKFLEVFG-UHFFFAOYSA-N 0.000 description 1
SCZGZDLUGUYLRV-UHFFFAOYSA-N (2-methylphenyl)hydrazine Chemical compound CC1=CC=CC=C1NN SCZGZDLUGUYLRV-UHFFFAOYSA-N 0.000 description 1
FRBUNLLUASHNDJ-UHFFFAOYSA-N (2-nitrophenyl)hydrazine Chemical compound NNC1=CC=CC=C1[N+]([O-])=O FRBUNLLUASHNDJ-UHFFFAOYSA-N 0.000 description 1
GFPJLZASIVURDY-UHFFFAOYSA-N (3-chlorophenyl)hydrazine Chemical compound NNC1=CC=CC(Cl)=C1 GFPJLZASIVURDY-UHFFFAOYSA-N 0.000 description 1
XAYCTBDPZIKHCW-UHFFFAOYSA-N (3-chloropyridin-2-yl)hydrazine Chemical compound NNC1=NC=CC=C1Cl XAYCTBDPZIKHCW-UHFFFAOYSA-N 0.000 description 1
KPIOFCJOKUHZPF-UHFFFAOYSA-N (3-methoxyphenyl)hydrazine Chemical compound COC1=CC=CC(NN)=C1 KPIOFCJOKUHZPF-UHFFFAOYSA-N 0.000 description 1
GPTOGZLZMLJZCV-UHFFFAOYSA-N (3-methylphenyl)hydrazine Chemical compound CC1=CC=CC(NN)=C1 GPTOGZLZMLJZCV-UHFFFAOYSA-N 0.000 description 1
IRZALWDJCUHVNE-UHFFFAOYSA-N (3-methylpyridin-2-yl)hydrazine Chemical compound CC1=CC=CN=C1NN IRZALWDJCUHVNE-UHFFFAOYSA-N 0.000 description 1
JFILLLZWNHOVHV-UHFFFAOYSA-N (3-nitrophenyl)hydrazine Chemical compound NNC1=CC=CC([N+]([O-])=O)=C1 JFILLLZWNHOVHV-UHFFFAOYSA-N 0.000 description 1
ZXBMIRYQUFQQNX-UHFFFAOYSA-N (4-fluorophenyl)hydrazine Chemical compound NNC1=CC=C(F)C=C1 ZXBMIRYQUFQQNX-UHFFFAOYSA-N 0.000 description 1
PVRSIFAEUCUJPK-UHFFFAOYSA-N (4-methoxyphenyl)hydrazine Chemical compound COC1=CC=C(NN)C=C1 PVRSIFAEUCUJPK-UHFFFAOYSA-N 0.000 description 1
XAMBIJWZVIZZOG-UHFFFAOYSA-N (4-methylphenyl)hydrazine Chemical compound CC1=CC=C(NN)C=C1 XAMBIJWZVIZZOG-UHFFFAOYSA-N 0.000 description 1
HFTSPKIAXHZROA-UHFFFAOYSA-N (6-chloropyridin-2-yl)hydrazine Chemical compound NNC1=CC=CC(Cl)=N1 HFTSPKIAXHZROA-UHFFFAOYSA-N 0.000 description 1
RDVGWJKUYXVTSO-UHFFFAOYSA-N (6-methylpyridin-2-yl)hydrazine Chemical compound CC1=CC=CC(NN)=N1 RDVGWJKUYXVTSO-UHFFFAOYSA-N 0.000 description 1
OLGOTNLCPQXGLS-UHFFFAOYSA-N 1-ethyl-4-methylpyrazole Chemical class CCN1C=C(C)C=N1 OLGOTNLCPQXGLS-UHFFFAOYSA-N 0.000 description 1
WITMXBRCQWOZPX-UHFFFAOYSA-N 1-phenylpyrazole Chemical compound C1=CC=NN1C1=CC=CC=C1 WITMXBRCQWOZPX-UHFFFAOYSA-N 0.000 description 1
OWVRXDVWWRDOEN-UHFFFAOYSA-N 1-tert-butyl-4-methylpyrazole Chemical class CC=1C=NN(C(C)(C)C)C=1 OWVRXDVWWRDOEN-UHFFFAOYSA-N 0.000 description 1
UTGILJSWZOJNBH-UHFFFAOYSA-N 2,3-dichloro-2-methylpropan-1-ol Chemical compound OCC(Cl)(C)CCl UTGILJSWZOJNBH-UHFFFAOYSA-N 0.000 description 1
CQQJSAWMJGLAMP-UHFFFAOYSA-N 2-(4-methylpyrazol-1-yl)pyridine Chemical class C1=C(C)C=NN1C1=CC=CC=N1 CQQJSAWMJGLAMP-UHFFFAOYSA-N 0.000 description 1
YWVMDMHSBOVNFR-UHFFFAOYSA-N 3-(4-methylpyrazol-1-yl)pyridine Chemical class C1=C(C)C=NN1C1=CC=CN=C1 YWVMDMHSBOVNFR-UHFFFAOYSA-N 0.000 description 1
MIGQGYPWOONPRH-UHFFFAOYSA-N 3-chloro-2-methylpropanal Chemical compound ClCC(C)C=O MIGQGYPWOONPRH-UHFFFAOYSA-N 0.000 description 1
HLTXSPXIYDZZRI-UHFFFAOYSA-N 4-(4-methylpyrazol-1-yl)pyridine Chemical class C1=C(C)C=NN1C1=CC=NC=C1 HLTXSPXIYDZZRI-UHFFFAOYSA-N 0.000 description 1
XXNOGQJZAOXWAQ-UHFFFAOYSA-N 4-chlorophenylhydrazine Chemical compound NNC1=CC=C(Cl)C=C1 XXNOGQJZAOXWAQ-UHFFFAOYSA-N 0.000 description 1
XBHHKVWZNGPYQD-UHFFFAOYSA-N 4-methyl-1-propan-2-ylpyrazole Chemical compound CC(C)N1C=C(C)C=N1 XBHHKVWZNGPYQD-UHFFFAOYSA-N 0.000 description 1
125000000590 4-methylphenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 1
KMVPXBDOWDXXEN-UHFFFAOYSA-N 4-nitrophenylhydrazine Chemical compound NNC1=CC=C([N+]([O-])=O)C=C1 KMVPXBDOWDXXEN-UHFFFAOYSA-N 0.000 description 1
NTSLROIKFLNUIJ-UHFFFAOYSA-N 5-Ethyl-2-methylpyridine Chemical compound CCC1=CC=C(C)N=C1 NTSLROIKFLNUIJ-UHFFFAOYSA-N 0.000 description 1
KNCHDRLWPAKSII-UHFFFAOYSA-N 5-ethyl-2-methylpyridine Natural products CCC1=CC=NC(C)=C1 KNCHDRLWPAKSII-UHFFFAOYSA-N 0.000 description 1
IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
238000005705 Cannizzaro reaction Methods 0.000 description 1
ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical group C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
AMIMRNSIRUDHCM-UHFFFAOYSA-N Isopropylaldehyde Chemical compound CC(C)C=O AMIMRNSIRUDHCM-UHFFFAOYSA-N 0.000 description 1
UQFQONCQIQEYPJ-UHFFFAOYSA-N N-methylpyrazole Chemical compound CN1C=CC=N1 UQFQONCQIQEYPJ-UHFFFAOYSA-N 0.000 description 1
239000002202 Polyethylene glycol Substances 0.000 description 1
239000004721 Polyphenylene oxide Substances 0.000 description 1
WTKZEGDFNFYCGP-UHFFFAOYSA-N Pyrazole Chemical compound C=1C=NNC=1 WTKZEGDFNFYCGP-UHFFFAOYSA-N 0.000 description 1
150000001242 acetic acid derivatives Chemical class 0.000 description 1
230000002378 acidificating effect Effects 0.000 description 1
239000003905 agrochemical Substances 0.000 description 1
150000001299 aldehydes Chemical class 0.000 description 1
239000003513 alkali Substances 0.000 description 1
230000002152 alkylating effect Effects 0.000 description 1
239000003125 aqueous solvent Substances 0.000 description 1
239000002585 base Substances 0.000 description 1
XKLVLDXNZDIDKQ-UHFFFAOYSA-N butylhydrazine Chemical compound CCCCNN XKLVLDXNZDIDKQ-UHFFFAOYSA-N 0.000 description 1
235000013339 cereals Nutrition 0.000 description 1
239000007795 chemical reaction product Substances 0.000 description 1
239000000460 chlorine Substances 0.000 description 1
229910052801 chlorine Inorganic materials 0.000 description 1
NEHMKBQYUWJMIP-NJFSPNSNSA-N chloro(114C)methane Chemical compound [14CH3]Cl NEHMKBQYUWJMIP-NJFSPNSNSA-N 0.000 description 1
125000004122 cyclic group Chemical group 0.000 description 1
238000006114 decarboxylation reaction Methods 0.000 description 1
238000000354 decomposition reaction Methods 0.000 description 1
230000007423 decrease Effects 0.000 description 1
238000007033 dehydrochlorination reaction Methods 0.000 description 1
229910001873 dinitrogen Inorganic materials 0.000 description 1
239000006185 dispersion Substances 0.000 description 1
239000004210 ether based solvent Substances 0.000 description 1
150000002170 ethers Chemical class 0.000 description 1
125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
WHRIKZCFRVTHJH-UHFFFAOYSA-N ethylhydrazine Chemical compound CCNN WHRIKZCFRVTHJH-UHFFFAOYSA-N 0.000 description 1
239000004009 herbicide Substances 0.000 description 1
150000003840 hydrochlorides Chemical class 0.000 description 1
239000004615 ingredient Substances 0.000 description 1
125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
CIXSDMKDSYXUMJ-UHFFFAOYSA-N n,n-diethylcyclohexanamine Chemical compound CCN(CC)C1CCCCC1 CIXSDMKDSYXUMJ-UHFFFAOYSA-N 0.000 description 1
125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
150000002823 nitrates Chemical class 0.000 description 1
229920000570 polyether Polymers 0.000 description 1
229920001223 polyethylene glycol Polymers 0.000 description 1
239000011736 potassium bicarbonate Substances 0.000 description 1
235000015497 potassium bicarbonate Nutrition 0.000 description 1
229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
229940086066 potassium hydrogencarbonate Drugs 0.000 description 1
238000002360 preparation method Methods 0.000 description 1
KJAQRHMKLVGSCG-UHFFFAOYSA-N propan-2-ylhydrazine Chemical compound CC(C)NN KJAQRHMKLVGSCG-UHFFFAOYSA-N 0.000 description 1
UKPBXIFLSVLDPA-UHFFFAOYSA-N propylhydrazine Chemical compound CCCNN UKPBXIFLSVLDPA-UHFFFAOYSA-N 0.000 description 1
125000003226 pyrazolyl group Chemical group 0.000 description 1
NWELCUKYUCBVKK-UHFFFAOYSA-N pyridin-2-ylhydrazine Chemical compound NNC1=CC=CC=N1 NWELCUKYUCBVKK-UHFFFAOYSA-N 0.000 description 1
RCIGDGBXEMECGY-UHFFFAOYSA-N pyridin-3-ylhydrazine Chemical compound NNC1=CC=CN=C1 RCIGDGBXEMECGY-UHFFFAOYSA-N 0.000 description 1
KRTLKPFLTASKCG-UHFFFAOYSA-N pyridin-4-ylhydrazine Chemical compound NNC1=CC=NC=C1 KRTLKPFLTASKCG-UHFFFAOYSA-N 0.000 description 1
230000009257 reactivity Effects 0.000 description 1
229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
235000017557 sodium bicarbonate Nutrition 0.000 description 1
239000011780 sodium chloride Substances 0.000 description 1
239000007787 solid Substances 0.000 description 1
125000001424 substituent group Chemical group 0.000 description 1
150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
MUQNAPSBHXFMHT-UHFFFAOYSA-N tert-butylhydrazine Chemical compound CC(C)(C)NN MUQNAPSBHXFMHT-UHFFFAOYSA-N 0.000 description 1
YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
ILWRPSCZWQJDMK-UHFFFAOYSA-N triethylazanium;chloride Chemical compound Cl.CCN(CC)CC ILWRPSCZWQJDMK-UHFFFAOYSA-N 0.000 description 1
238000005406 washing Methods 0.000 description 1

Classifications

- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
- C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
- C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D231/12—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
- C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
- C07D401/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings directly linked by a ring-member-to-ring-member bond

Landscapes

Chemical & Material Sciences (AREA)
Organic Chemistry (AREA)
Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Plural Heterocyclic Compounds (AREA)
Catalysts (AREA)
Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)

DE8989310624T 1988-10-26 1989-10-17 Verfahren zur herstellung von 4-methylpyrazolen. Expired - Fee Related DE68906638T2 (de)

Applications Claiming Priority (2)

Application Number	Priority Date	Filing Date	Title
JP27034588		1988-10-26
JP1236173A JP2861103B2 (ja)	1988-10-26	1989-09-12	４―メチルピラゾール類の製造方法

Publications (2)

Publication Number	Publication Date
DE68906638D1 DE68906638D1 (de)	1993-06-24
DE68906638T2 true DE68906638T2 (de)	1993-09-16

Family

ID=26532524

Family Applications (1)

Application Number	Title	Priority Date	Filing Date
DE8989310624T Expired - Fee Related DE68906638T2 (de)	1988-10-26	1989-10-17	Verfahren zur herstellung von 4-methylpyrazolen.

Country Status (5)

Country	Link
EP (1)	EP0366328B1 (ja)
JP (1)	JP2861103B2 (ja)
KR (1)	KR0133855B1 (ja)
DE (1)	DE68906638T2 (ja)
ES (1)	ES2055089T3 (ja)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number	Priority date	Publication date	Assignee	Title
FR2679556B1 (fr) *	1991-07-24	1993-09-24	Poudres & Explosifs Ste Nale	Procede de synthese de pyrazoles 1,4-disubstitues.
DE4328228A1 (de) *	1993-08-23	1995-03-02	Basf Ag	Verfahren zur Herstellung von Pyrazol und dessen Derivaten
DE4415484A1 (de) *	1994-05-03	1995-11-09	Basf Ag	Verfahren zur Herstellung von 1-(Het)aryl-3-hydroxy-pyrazolen
US5976475A (en) *	1997-04-02	1999-11-02	Clean Diesel Technologies, Inc.	Reducing NOx emissions from an engine by temperature-controlled urea injection for selective catalytic reduction
DE19829616A1 (de) *	1998-07-02	2000-01-05	Bayer Ag	Verfahren zur Herstellung von 1-Alkyl-pyrazol-5-carbonsäureestern
KR20080000660A (ko)	2005-04-21	2008-01-02	오르펀 메디칼, 인크.	초순수 4-메틸피라졸의 제조 방법

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number	Priority date	Publication date	Assignee	Title
FR2115062B1 (ja) *	1970-11-26	1974-04-12	Fuveau Sa
DE2922591A1 (de) *	1979-06-02	1980-12-04	Basf Ag	Verfahren zur herstellung von pyrazolen
DE3122261A1 (de) *	1981-06-04	1982-12-23	Bayer Ag, 5090 Leverkusen	Verfahren zur herstellung von pyrazolen

1989
- 1989-09-12 JP JP1236173A patent/JP2861103B2/ja not_active Expired - Fee Related
- 1989-10-17 EP EP89310624A patent/EP0366328B1/en not_active Expired - Lifetime
- 1989-10-17 DE DE8989310624T patent/DE68906638T2/de not_active Expired - Fee Related
- 1989-10-17 ES ES89310624T patent/ES2055089T3/es not_active Expired - Lifetime
- 1989-10-23 KR KR1019890015223A patent/KR0133855B1/ko not_active IP Right Cessation

Also Published As

Publication number	Publication date
JP2861103B2 (ja)	1999-02-24
KR0133855B1 (ko)	1998-04-23
EP0366328A1 (en)	1990-05-02
KR900006294A (ko)	1990-05-07
JPH02191258A (ja)	1990-07-27
ES2055089T3 (es)	1994-08-16
EP0366328B1 (en)	1993-05-19
DE68906638D1 (de)	1993-06-24

Legal Events

Date	Code	Title	Description
1994-06-16	8364	No opposition during term of opposition
2006-08-17	8339	Ceased/non-payment of the annual fee

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EP0715622B1 (de)	1998-04-22	Verfahren zur herstellung von pyrazol und dessen derivaten
DE3780669T2 (de)	1993-01-21	2-pyrazolin-5-ones und ein verfahren zu deren herstellung.
DE3733755C2 (ja)	1989-11-16
DE68906638T2 (de)	1993-09-16	Verfahren zur herstellung von 4-methylpyrazolen.
CH711995B1 (de)	2018-01-15	Verfahren zur Herstellung von 3-Fluoralkyl-1-methylpyrazol-4-Carbonsäure und eines Pestizids.
DE2166398B2 (de)	1977-10-27	4,5-tetrazolo- eckige klammer auf 1,5-a eckige klammer zu chinoline und verfahren zu ihrer herstellung
DD292000A5 (de)	1991-07-18	Pyrimidinyl-piperazinyl-alkylazolderivate mit anxiolitischer und/oder beruhigender aktivitaet
CH617427A5 (ja)	1980-05-30
EP0839138A1 (de)	1998-05-06	Verfahren zur herstellung von n-substituierten 3-hydroxypyrazolen
DE60003846T2 (de)	2004-06-03	Verfahren zur herstellung von substituierten pyrazolen
DE69313771T2 (de)	1998-02-12	Carbazolon - Derivate und Verfahren zu ihrer Herstellung
DE1900125A1 (de)	1969-09-04	Neue heterocyclische Verbindungen und Verfahren zu ihrer Herstellung
DE69405023T2 (de)	1998-01-15	Verfahren zur Herstellung wässriger Nicotinaldehyde
AT397961B (de)	1994-08-25	Verfahren zur grossproduktion von 1-((1-(2- (trifluormethyl)-4-pyrimidinyl)-4-piperidinyl)- methyl)-2-pyrrolidinon
DE1420011B1 (de)	1971-05-19	Verfahren zur Herstellung von 4,5-Dihalogenpyridazonen
DE68926016T2 (de)	1996-09-19	Halogeno-4-Methylpyrazole und Verfahren zu ihrer Herstellung
DE3418382A1 (de)	1984-11-22	Verfahren zur herstellung von 1,8-dihydroxy-10-acyl-9-anthronen
DD242223A5 (de)	1987-01-21	Verfahren zur herstellung von substituierten phenylhydrazinen
JPH0720958B2 (ja)	1995-03-08	ピラゾ−ルスルホンアミド誘導体、製法および除草剤
DE2239892A1 (de)	1973-03-01	Mittel zur bekaempfung von pflanzenpathogenen organismen